EP2342308B1 - Générateur de gaz de synthèse combiné - Google Patents

Générateur de gaz de synthèse combiné Download PDF

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Publication number
EP2342308B1
EP2342308B1 EP09817033.5A EP09817033A EP2342308B1 EP 2342308 B1 EP2342308 B1 EP 2342308B1 EP 09817033 A EP09817033 A EP 09817033A EP 2342308 B1 EP2342308 B1 EP 2342308B1
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Prior art keywords
ghr
pox
stage
syngas
stream
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German (de)
English (en)
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EP2342308A2 (fr
EP2342308A4 (fr
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Rodney J. Allam
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Gtlpetrol LLC
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Gtlpetrol LLC
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C01B2203/0894—Generation of steam
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • C01B2203/1282—Mixing of different feed components using static mixers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to combined synthesis gas generators.
  • a hydrocarbon feed and oxygen and optionally steam is provided to a partial oxidation reactor, and the product of the partial oxidation reactor and/or a portion of the feed stream are then provided to a catalytic reformer.
  • heat is recovered to raise steam in a separate unit.
  • High pressure and high temperature piping connect the various reactors, which also include separate foundations or separate support structures.
  • US 4,822,521 relates to an integrated process and apparatus for the primary and secondary catalytic steam reforming of hydrocarbons.
  • the invention is directed to a system for producing syngas containing at least hydrogen and carbon monoxide, comprising:
  • a feed stream is processed to produce synthesis gas (e.g., streams including hydrogen and carbon monoxide) streams.
  • the processed feed streams may include a variety of feed streams that include methane, such as natural gas, hydrocarbon fuels, methane rich gases such as coalbed methane or biogas (e.g., stream produced from the anaerobic decay of matter).
  • the feed streams may include liquid or gaseous hydrocarbons, such as natural gas and liquefied petroleum gas and distillates.
  • the combined synthesis gas generation system may integrate a partial oxidation reactor (POX) and a gas heated catalytic reformer (GHR) (e.g., a convectively heated steam/hydrocarbon catalytic reformer) such that the synthesis gas produced by the POX is mixed with the synthesis gas from the GHR.
  • the combined stream may be used to heat the GHR (e.g., since the synthesis gas produced by the POX and the GHR may have a temperature sufficient to heat the feed entering the GHR and/or steam entering the GHR and provide the endothermic heat of reaction required to covert the steam and hydrocarbon feed in the GHR to produce synthesis gas).
  • the feed gases to the POX and/or the GHR may include a stream of CO 2 to produce a required CO to H2 ratio in the combined synthesis gas generation stream.
  • the combined stream may leave the shell side of the GHR cooled and be further cooled in a waste heat boiler (WHB).
  • WHB waste heat boiler
  • the WHB maybe an integrated stage of the synthesis gas generation system.
  • the WHB may be a separate reactor.
  • the heat from the combined stream leaving the shell side of the GHR may heat boiler feed water to produce steam to be utilized by the POX and/or the GHR.
  • the steam may be produced by the WHB at a pressure sufficiently high to allow the steam to be mixed with the hydrocarbon fuel for the GHR and/or the POX.
  • the resulting steam and feed stream may be further preheated by an external means.
  • the POX, GHR, and WHB are built as three separate units, for example, separate pressure vessels linked by pipes and located in a support structure.
  • the general arrangement requires expensive internally insulated piping and/or high alloy steel piping, and associated supports, etc.
  • a combined synthesis gas generation system may reduce costs (e.g., since less expensive piping may be used and since connections between previously separate units may be eliminated) while maintaining the process and operating and maintenance and safety features desired in a synthesis gas generation system.
  • Another feature of a single reactor unit for the sequential operations of partial oxidation, auto-thermal reforming and optionally waste heat recovery, is to generate steam internally so that the synthesis gas stream passes through the composite unit without requiring the synthesis gas to pass through any piping connection between the units.
  • FIG. 1 illustrates an example synthesis gas generation system 100 and FIGS. 2 and 3 illustrate portions of the synthesis gas generation system 100.
  • the synthesis gas generation system 100 illustrated is a three-stage synthesis gas generation system in which the POX stage 1, GHR, stage 5, and WHB stage 14 are arranged vertically.
  • a vertical arrangement may decrease the footprint required for the combined synthesis gas generation system when compared with conventional combined gas generation systems and/or conventional separate unit gas generation systems. Reducing the footprint of the system may be more cost-effective (e.g., reduce land requirements), allow the system to be positioned in reduced footprint environments, and/or allow the combined synthesis gas generation system (e.g., together with other components or the overall process) to be fabricated as a single module of compact dimensions and minimum weight.
  • the POX stage 1 is positioned proximate the bottom of the synthesis gas generation system 100.
  • the WHB stage 14 is positioned proximate the top of the synthesis gas generation system 100 and the GHR.
  • stage 5 is positioned between the WHB stage and the POX stage.
  • the POX stage 1 may include a POX burner assembly 2 that includes a feed inlet 3 and another inlet 4. An oxygen stream and/or a steam stream may be provided to the POX stage 1 through the other inlet 4.
  • the burners of the burner assembly 2 may be configured to inhibit zones of little or insignificant mixing in the POX stage 1, For example, the burners may be configured to produce a stable vortex flow.
  • a mixing space 6 may reside above the POX stage 1 and below the tubes 7 of the GHR stage 5.
  • the mixing stage 6 may include sufficient volume for efficient mixing of the high temperature gases produced by the burner 2 and/or for sufficient residence time for the high temperature reactions such as the partial oxidation and shift reactions to take place. This may produce the maximum yield of synthesis gas with the required CO to H2 ratio while minimizing the production of solid carbon particles.
  • the tubes 7 may be at least partially filled with a catalyst appropriate for the catalytic steam reformation of feed stream entering the GHR stage through GHR inlet 19.
  • the tubes 7 are fixed into a tube sheet 7' at the cold end and have no fixing at the hot end allowing unrestricted expansion at operating temperature.
  • the tubes 7 of the GHR stage 5 may include a restriction 9 (e.g., an outlet nozzle) to increase the gas discharge velocity. Increasing the gas discharge velocity may promote good mixing between the POX and GHR product gas streams. The mixing may also be promoted by arranging a perforated plate 8 in the combined gas flow stream (e.g., combined gas from the tubes 7 of the GHR stage 5 and the POX stage 1). The plate 8 is located above the outlet nozzles 9 of the GHR tubes 7.
  • a particulate layer e.g., particulate layer 560 in FIG. 5
  • may include solid granules or solid formed pellets 560 may be placed above the perforated plate.
  • These granules or pellets may include an inert material such as alumina or silica, or other inert materials capable of withstanding the operating temperature.
  • the granules or pellets may filter at least a portion of the carbon particles produced in the POX reactor to prevent excessive carryover to the GHR reactor.
  • the carbon trapped on the surface of these granules or pellets will quickly react with excess steam present in the combined synthesis gas stream (e.g., at the operating temperatures of greater than 1000° C), and this continuous removal of deposited solid carbon will inhibit blockage due to the solid carbon.
  • the granules or pellets may include catalysts, such as catalysts to promote the water gas shift reaction. See eqn. (1).
  • the tubes 7 of the GHR stage 5 may be coupled (e.g., affixed) to a tube sheet 7'.
  • the tube sheet 7' may be supported on a support ring 10 that is coupled (e.g., welded) to the shell 11 of the POX stage 1 and GHR stage 5.
  • the position of the GHR tube sheet 7' on the support ring 10 may be retained by coupling members 21 (e.g., studs, bolts, etc.).
  • a GHR feed stream which may include steam and a portion of the hydrocarbon feed and/or CO 2 may flow into the GHR stage 5 through a GHR inlet 19.
  • the GHR inlet may include a flexible portion 24 to, for example, compensate for thermal expansion when the unit is at its operating temperature.
  • the GHR stage 5 may include a header cover 20 proximate a top of a GHR stage.
  • the header cover 20 may be coupled, off center, to a top flange of the GHR stage 5 using a coupling member 22 (e.g., studs, bolts, etc.) so that it covers (at least a portion of) the top section of the tube sheet 7'and covers all of the GHR tubes 7.
  • the entire top section of the GHR tubes 7 may be covered by the header cover 20.
  • An internal portion of the inlet nozzle 19 may be detached from the vessel wall 11 to facilitate the removal of the GHR top header 20 and/or allow access to each of the catalyst filled reactor tubes.
  • the GHR stage 5 includes a segmentally baffled shell side.
  • the shell side of the GHR stage 5 has a segmental cut-out 12 in the tube sheet to allow the synthesis gas stream to pass out of the shell side of the GHR stage 5 into the space 13 below the WHB stage 14.
  • the WHB stage 14 includes, coupled to the shell side, a boiler feed-water inlet pipe 15 (e.g., proximate the base of the WHB stage) and an outlet steam or steam plus water carryover pipe 16 (e.g., proximate the top of the WHB stage).
  • the WHB stage 14 includes tubes for the passage of the total synthesis gas product stream in heat transfer contact with the evaporating water on the shell side.
  • the WHB stage 14 includes a top cover 17 with a synthesis gas outlet pipe 18.
  • the GHR feed stream may be provided through GHR inlet 19 to the area 20', which is enclosed by the header cover.
  • the GHR feed stream may flow from the area 20' enclosed by the header cover 20 into the tubes 7.
  • the header cover may inhibit communication between the inlet feed in pipe 19 and the product gas in space 13. At least portions of the GHR feed stream may undergo catalytic steam reformation to produce synthesis gas.
  • the product stream may exit through the nozzles 9 of the tubes 7 to mix with the gases from the POX stage of the combined synthesis gas generation system.
  • This combined stream may flow through the perforated plate 8 to the shell side of the GHR stage to provide heat to the tubes for the catalytic steam reformation of the GHR feed stream in the tubes 7.
  • the combined gas stream may be cooled.
  • the cooling and heat transfer from the shell side synthesis gas flow may be enhanced by including regularly spaced horizontal baffles (e.g., vertically separated, which direct the shell side flow over the outside of the tubes 7 in an optimum manner consistent with constraints of pressure drop through the shell side of the GHR 5).
  • the baffles have segmental cutouts alternatively arranged to facilitate the flow of shell side gas from one baffle space to another.
  • the baffle arrangement allows the cut-out in the tube sheet to coincide with baffle size and location relative to the tube bundle so that the shell side gas flow may exit though the tube sheet cut-out 12.
  • a disc and doughnut baffle arrangement may be utilized.
  • the cooled gas stream may exit the shell side of the GHR stage 5 at opening 12 to flow into the space 13 disposed between the WHB stage 14 and the GHR stage 5.
  • the cooled gas stream may then flow into the tube side of the WHB stage 14 and provide heat to produce steam from the feed water from inlet 15, which may further cool the cooled combined gas stream.
  • the produced steam or steam plus water may exit the shell side of the WHB at outlet 16.
  • Part or all of the steam stream optionally with further professing which may include further heating could be provided to the GHR stage 5 and/or the POX stage 1.
  • the further cooled combined synthesis gas stream may exit the WHB stage and/or the combined synthesis gas system at synthesis gas outlet 18.
  • the exposed metallic portions or portions thereof may include a protective coating 23 (e.g., the coating may be coated, the coating may be a top layer of the portions, the coating may be a removably coupled layer, etc.).
  • the protective coating 23 may be substantially gas impermeable and/or be applied after the GHR stage 5 has been installed with header cover 20. The protective coating 23 may be removed if the GHR bundle needs to be replaced in the future. Protective insulation may at least partially cover the coupling members 21 and 22.
  • the lower side of the GHR tube sheet 7', or at least portions thereof, may be coated with a gas impermeable coating 24.
  • the coating 24 may allow the tube sheet to be constructed from a less expensive material than the GHR tubes 7 (e.g., the GHR tubes may include nickel alloys such as 693 or 617.
  • the vessel wall in the POX stage 1 and GHR stage 5 may be internally insulated with an insulation layer 25.
  • the insulation layer 25 may include a permanent ceramic insulation.
  • the vessel shell in the region of the space 13 may be internally insulated with an insulation layer 26, which may include, in some implementations, a permanent ceramic insulation.
  • the stages may be arranged horizontally or obliquely.
  • the POX stage may be positioned proximate the top of a synthesis gas generation system.
  • the GHR stage may be positioned proximate (e.g., adjacent, bellow, etc.) the POX stage. with the WHB below the GHR stage.
  • nozzle 16 will be above nozzle 15 and proximate to tube sheet 27
  • the system may be arranged in a vertical or oblique configuration with the POX on top, followed by the GHR and with the WHB at the bottom. The vertical arrangement shown in FIG.
  • a pipe may be a conduit.
  • other insulation layers 25 and/or 26 may include a different type of insulation.
  • a cross-sectional area of a POX stage and a GHR stage may be approximately similar in size.
  • the combined synthesis gas generation system may be a single pressurized vessel that includes three stages.
  • the steam produced by the WHB stage may be combined with feed stream and/or provided to a preheater. The steam produced by the WHB stage may not be provided to a piping system external to the combined synthesis gas system, but rather provided internally to the POX stage and/or the GHR stage.
  • FIG. 4 illustrates an example process for producing synthesis gas using a combined synthesis gas generation system, such as the combined synthesis gas generation system illustrated in FIG. 1 .
  • a feed stream may be partially oxidized in a partial oxidation stage of a three-stage reactor using at least one burner proximate a bottom of the three-stage reactor (operation 402).
  • a natural gas stream, an oxygen stream, and/or steam may be provided to a POX stage of a three-stage reactor.
  • a temperature distribution in the POX stage greater than a specified range may be inhibited (operation 404).
  • the burner(s) of a POX may be designed to achieve a substantially even reaction temperature in the POX stage.
  • Limiting zones of little or insignificant mixing may increase yields of synthesis gas, reduce costs of producing synthesis gas, and/or promote even reaction temperatures in the POX stage, for example.
  • Free carbon and/or soot production may be inhibited (operation 406).
  • the burner(s) of the POX may be designed or selected such that free carbon or soot production is minimized.
  • the gases in the POX stage of the three-stage reactor may be allowed to mix (e.g., due to the flow pattern of the gases) such that zones of little or insignificant mixing in the POX stage are inhibited (operation 408).
  • the burners of the POX may be positioned such that zones of little or insignificant mixing is minimized or inhibited.
  • a stable vortex flow in the POX stage may be produced to inhibit zones of little or insignificant mixing.
  • the POX stage may have sufficient volume for efficient mixing of the high temperature gases produced by the burner to take place and for sufficient residence time for the high temperature reactions to take place, which may maximize the output of synthesis gas and minimize the production of solid carbon particles (e.g., zero or minimal carbon particle production).
  • the gases from the POX stage and the gases from the tubes of the GHR stage may be allowed to mix (operation 410).
  • the gases from the POX stage and the GHR stage may be allowed to mix in the mixing zone disposed between the tubes of the GHR and the POX stage.
  • the gas from the tubes of the GHR may include synthesis gas produced by catalytic steam reformation of the feed stream and the steam stream and/or CO 2 stream entering the tubes of the GHR stage.
  • Product gas from the GHR stage may exit from nozzles of the tubes to promote mixing between the gases from the POX and the tubes of the GHR (operation 412).
  • the combined gas stream may flow through a perforated plate (operation 414).
  • the combined gas stream may flow through a perforated plate positioned proximate the mixing zone to the shell side of the GHR stage.
  • the perforated plate may support a particulate layer which can act as a carbon removal device and/or a catalytic section, to achieve equilibrium for the water gas shift reaction and/or cool the combined synthesis gas mixture.
  • the shell side of the GHR may be baffled. Allowing the combined gas stream to flow through the perforated plate may impose a pressure drop across the perforated plate, which may cause a more even flow (e.g., when compared to flow without use of a perforated plate) across the perforated plate over a cross-section of the mixing space.
  • Steam and feed and/or CO2 in the tubes of the GHR stage may be heated (operation 416).
  • the combined gas stream in the shell side of the GHR may provide heat to heat the stream in the tube side of the GHR stage.
  • the cooled combined gas stream may flow from the shell side of the GHR stage to the WHB stage (operation 418).
  • the feed water to the WHB may be heated using the cooled gas to produce steam to be provided to the GHR stage and/or the POX stage (operation 420). Excess steam may be used for power production.
  • the cooled combined gas stream may be further cooled by providing the heat to produce steam in the WHB.
  • the cooled combined gas stream that includes synthesis gas may flow from the WHB (operation 422).
  • Process 400 may be implemented by various systems, such as system 100.
  • various operations may be added, deleted, or modified.
  • operations 418, 420, and/or 422 may not be performed by the combined synthesis gas system.
  • the steam stream produced may be provided to a pre-heater and/or mixed with a portion of a feed stream.
  • the process 400, or portions thereof may be performed by a two-stage reactor (e.g., a reactor that includes a POX stage and a GHR stage).
  • Fig. 5 illustrates a portion of an example synthesis gas generation system 500.
  • the synthesis gas generation system 500 includes a two-stage reactor with an integrated POX stage 510 and GHR stage 520.
  • a feed stream, oxygen stream, and/or steam stream may be provided to a burner 512 of the POX stage 510.
  • the feed stream may be partially oxidized to produce synthesis gas.
  • a feed stream and steam stream and/or CO2 stream may be provided to the tube side of a GHR stage 520.
  • the tubes 522 which include a catalyst, at least a portion of the feed stream in the tubes may be catalytically steam reformed to produce synthesis gas.
  • the gas stream from the tubes 522 optionally with nozzles 9 of the GHR stage 520 and the gases in the POX stage 510 may be mixed and allowed to flow through the perforated plate 530.
  • the combined gas stream may flow through the perforated plate 530 and the particulate layer 560 to the shell side of the GHR stage.
  • Heat from the combined gas stream may be provided to the stream in the tubes of the GHR stage. Allowing the heat from the combined gas stream to be utilized to heat the stream in the tubes of the GHR side may provide cost-savings and produce a higher yield of synthesis gas.
  • the shape of the top of the POX stage 510 may be such that the refractory internal vessel lining 550 is built up (e.g., so that protrusion(s) into a vessel cavity exist) and/or protrusions may be coupled to an internal area of the vessel so that the tubes 522 are approximately evenly distributed across the exit cross-section of the POX gas flow, as illustrated in FIGS. 5-7 .
  • FIG. 6 illustrates a cross-sectional view of a top portion 600 of a POX stage. As illustrated, two baffle segments 610 would be disposed proximate edges of the cross-section, assuming there were no tubes 620 through the baffle segments. As illustrated in Fig.
  • the segments 710 would be an annular ring and there may also be a circular empty area in the perforated plate 540 above the GHR outlet nozzles.
  • a perforated plate 530 may be disposed proximate the ends of the GHR tube 522 (e.g., above the outlet nozzles 9 of the tubes).
  • the GHR tubes may penetrate the perforated plate 530.
  • the plate 530 may include apertures for the GHR tube penetrations and a second set of apertures, which may be smaller.
  • the gas stream from the mixing zone may pass through the second set of apertures to the shell side of the GHR.
  • the second set of apertures may cause a further pressure drop and/or ensure even flow over the cross-section of the POX/GHR mixing space.
  • the combined synthesis gas flow may be asymmetric as the gas flow enters the baffled heat exchange section.
  • a vessel cross-sectional area (e.g., diameter) between the POX and GHR stage may be similar or different.
  • the vessel may narrow between the POX stage and the GHR stage and/or through the GHR stage.
  • the vessel may have an approximately consistent cross-sectional area across the length of the vessel.
  • a shell side of the GHR stage may include a layer of packing material, such as an inert ceramic-shaped packing material, (e.g., in space 560 illustrated in FIG. 5 ).
  • the packing may be disposed above the perforated plate and may trap carbon particles produced by the POX burner (e.g., carbon particles may be produced particularly during start-up of the system as it is being brought up to operating temperature).
  • a feature of the system may be that when the system is operated at temperatures of above approximately nine hundred degrees Celsius, any carbon trapped on the packing layer will be gasified to CO and H 2 when reacted by reaction with steam.
  • the POX burner may be a single unit or multiple units each with a separate oxygen, feed, and/or steam inlets.
  • the POX burner(s) may be disposed proximate the bottom head of the POX stage and fire vertically upwards.
  • the burner(s) may be designed to promote back mixing of hot product synthesis gas into the high temperature primary oxygen/hydrocarbon reaction zone to ensure even reaction temperature range.
  • the burner(s) may also be designed to minimize, inhibit, and/or eliminate free carbon or soot production by the burner.
  • recirculation may be caused by the burner design and may provide a discharge gas flow pattern which provides a stable vortex flow immediately above each burner.
  • the stable vortex flow may provide a large recirculation gas flow pattern back into the reaction zone of the burner.
  • there may be a minimum level of bulk recirculation flow in the main area of the POX stage. For example, greater than 90% of the POX synthesis gas may have a residence time of 4 seconds or more to allow time to maximize production of synthesis gas in the POX reactor.
  • Another feature of the system may include that the mixing of the GHR tubes outlet synthesis gas flow and the POX synthesis gas flow may be independent of the flow patterns in the POX burner system. Thus, the appropriate flow pattern for each mixing stage may be implemented.
  • a primary mechanism for mixing the GHR outlet synthesis gas from each catalyst filled tube is through the use of a restriction nozzle proximate an end of each tube.
  • the gas exiting the nozzle may have an average outlet velocity of at least approximately 20 meters/second and/or from approximately 30 to 80 meters/second. These high velocity gas streams may cause a majority of the surrounding gas to mix with the GHR synthesis gas product exiting the tubes.
  • GHR reactor vessel stage may be arranged with GHR tubes in a baffled heat exchanger configuration using either a segmental baffle or a disc and doughnut arrangement of baffles.
  • Another feature of the system may include a concentric tube surrounding each of the GHR tubes 7 such that the combined synthesis gas leaving the layer 560 enters these concentric spaces and provides the heat required for the GHR reforming reactions.
  • the concentric tubes can then terminate at the top baffle (either segmental or concentric) at the cold end of the GHR so that the combined synthesis gas stream can pass through the opening 12 into the space 13 between the GHR and the WHB.
  • Another feature of the system may include significant cost savings (e.g., decreasing piping requirements, decreased footprint, more efficient heat recovery and utilization, etc.),
  • piping is not required for the product gas streams (e.g., synthesis gas) to flow between multiple vessels.
  • the piping required for separate vessels is commonly high temperature, internally insulated with large diameter high pressure external steel pipe which must be either water jacketed to keep the temperature constant or monitored for any possible local heating due to problems with the internal insulation.
  • Reduction of the need for this type of expensive piping may decrease costs of set-up (e.g., due to easier installation, less piping required, etc.) and production of synthesis gas (e.g., since the expensive piping will not need to be monitored, repaired, or replaced).
  • a minimum vertical and a horizontal separation is required between the vessels (e.g., by government and/or industry standards, such as DOW Fire and Safety Standards) to accommodate the high temperature synthesis gas piping connections.
  • a single vessel can be free-standing with adequate clearance for removal of the burners from the base of the vessel. No supporting steel structure may be necessary and/or significantly less supporting steel may be required when compared with systems that utilize separate vessels.
  • the cost of a single unit is significantly less than three units. For example, there are two high-pressure vessel heads on a single unit, rather than six on three separate units.
  • cost savings and time savings may be realized since one vessel coding and approval is required when utilizing a single unit, as opposed to three units or two units.
  • Another feature of the system includes that a single unit can be built as a modular fully fabricated, transportable assembly which may also include other upstream and downstream components at a much larger through-put than a three-vessel configuration.
  • Another feature includes decreased risk of refractory failure, since the refractory arrangement, location and quantity may be more favorable than a design with internally insulated interconnecting piping.
  • Another feature of the system may include that approximately the same or a fewer number of significant problems are associated with starting up and operating with a single vessel. In fact, fewer problems may be associated with a single vessel when compared to two or three separate units, since in practice the entire three-vessel synthesis gas train must be started up, shut down and operated as a single unit with no isolation valves between the three units. Another feature may be that sensors to monitor plant performance may be easily positioned within the single vessel envelope. Furthermore, maintenance and inspection may be facilitated in the single-vessel configuration, when compared with maintaining and inspecting multiple units.
  • Another feature may include the stable vortex mixing of the POX stage.
  • the systems described in U.S. Patent No. 4,741,885 include a swirling arrangement of POX burners along a length of a vessel to induce a vortex flow with an upward central component which has a cross-section corresponding to the cross-section of the tube area in the GHR.
  • the use of multiple burners arranged tangentially around the periphery of the POX section and inclined at an angle to the radial axis at each burner position and also inclined upwards cause an upward swirling motion to be induced in the cavity of the POX stage.
  • dead zones, or areas with insignificant mixing, or flow velocities will occur.
  • the dead zones may cause an uneven reaction temperature profile in the POX stage and/or decreased yield of synthesis gas.
  • the system described in US 4,741,885 cause a pressure differential across the unit. This pressure differential is highly undesirable.
  • a further disadvantage is that the vortex formation is in the whole body of the POX space and serves to induce synthesis gas product at lower temperature to be drawn down into the POX space, thus locally lowering the POX space temperature and preventing the maximum conversion of the POX burner gases to synthesis gas due to the variation in temperature and residence time caused by this arrangement.
  • the streams may include one or more other components.
  • the feed stream may include other components such as other hydrocarbons (e.g., ethane, propane, butane, pentane, etc.), other carbon-containing compounds (e.g., carbon dioxide, carbon monoxide, alcohols, etc.), organic compounds, sulfur containing compounds (e.g., organic sulfur compounds , hydrogen sulfide, etc.), nitrogen, argon, etc.
  • the feed stream may be natural gas, gases associated with the production of crude oil, combustible off-gasses from other processes such as refinery operations, liquid hydrocarbons, etc.
  • the sulfur compounds in natural gas may be removed or at least partially removed to prevent catalyst damage, particularly in the GMR.
  • the synthesis gas may also include other components, such as inert gases (e.g., nitrogen or argon).
  • an oxygen stream may include inert gases or nitrogen, in addition to oxygen.
  • streams are described as gas streams or including gases, other forms of matter may also exist in the streams.
  • the stream may include liquid.
  • streams in the WHB stage may include water and steam or a liquid hydrocarbon may be used as a feed stream to the POX burner.

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  • Chemical & Material Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Combustion & Propulsion (AREA)
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Claims (7)

  1. Système de production de gaz de synthèse contenant au moins de l'hydrogène et du monoxyde de carbone, comprenant :
    un réacteur d'oxydation partielle (POX) (1) qui fait réagir de façon exothermique une première partie d'un flux d'alimentation en hydrocarbures avec un gaz oxydant comprenant de l'oxygène moléculaire et éventuellement de la vapeur et du dioxyde de carbone dans un premier réacteur pour obtenir un produit de gaz de synthèse généré par voie exothermique, où le flux d'alimentation inclut du méthane ;
    un reformeur chauffé au gaz (GHR) (5) positionné de façon adjacente au POX et qui reforme de façon endothermique une deuxième partie du flux d'alimentation en hydrocarbures avec de la vapeur et éventuellement du dioxyde de carbone sur un catalyseur dans un reformeur à échange de chaleur pour obtenir un produit de gaz de synthèse reformé par voie endothermique, où la chaleur utilisée dans la génération du gaz de synthèse reformé par voie endothermique est dérivée de la chaleur libérée par le refroidissement du flux combiné du gaz de synthèse produit par le POX et le GHR ;
    une zone de mélangeage (6) disposée entre les tubes (7) des stades GHR et POX, où les gaz du stade POX et du stade GHR sont mélangés ; et
    une chaudière à chaleur effluente (WHB) (14) positionnée de façon adjacente au GHR qui génère de la vapeur en utilisant la chaleur dérivée par refroidissement du flux de gaz de synthèse combiné depuis le GHR ; et
    où le POX, le GHR et la WHB sont contenus dans un unique réceptacle sous pression indépendant de la tuyauterie entre le POX, le GHR et la WHB, et présentant un mélangeage interne entre le gaz de synthèse du POX et le gaz de synthèse du GHR pour obtenir un flux de gaz de synthèse combiné qui s'écoule par-delà les tubes du GHR en fournissant de la chaleur pour les réactions de reformage endothermique et dépasse les flux de gaz de synthèse combinés pour sortir d'un côté enveloppe du GHR et entrer dans la WHB pour fournir de la chaleur pour la production de vapeur,
    caractérisé en ce que
    une disposition interne du GHR inclut une plaque tubulaire (7') qui inclut une ouverture (12) à travers laquelle un débit de gaz de synthèse totale peut passer en étant isolé d'un flux d'alimentation du GHR total via un couvercle (20) fixé et recouvrant une partie de la plaque tubulaire dans laquelle les tubes du GHR sont fixés.
  2. Système selon la revendication 1, où le POX, le GHR et la WHB sont disposés verticalement, le POX étant positionné sous le GHR et la WHB étant positionnée au-dessus du GHR.
  3. Système selon la revendication 1, où une zone de mélangeage est ménagée entre le POX et le GHR pour le mélangeage du produit de gaz de synthèse obtenu entre le POX et le GHR de sorte que les flux de gaz combinés entrant du côté enveloppe du GHR soient à une température uniforme.
  4. Système selon la revendication 1, où le GHR comprend une entrée de GHR (19) pour un flux d'alimentation totale incluant des éléments flexibles (24) qui compensent la dilatation thermique.
  5. Système selon les revendications 1 ou 4, comprenant en outre une connexion interne entre une buse d'entrée de gaz d'alimentation de GHR total et un couvercle de plaque tubulaire de GHR qui peut être retiré pour exposer les tubes du GHR.
  6. Système selon les revendications 1, 4 ou 5, où un ensemble de GHR peut être retiré d'un réceptacle sous pression en retirant la WHB pour exposer le GHR.
  7. Système selon la revendication 1, où chacun des tubes de GHR inclut une restriction telle qu'une buse (9) sur une extrémité de sortie pour augmenter une vitesse de déchargement de gaz de synthèse par le GHR, située au moins à proximité d'une zone de mélangeage entre le POX et le GHR.
EP09817033.5A 2008-09-29 2009-09-29 Générateur de gaz de synthèse combiné Active EP2342308B1 (fr)

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CN (1) CN102165047B (fr)
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ES (1) ES2637015T3 (fr)
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WO2018093604A1 (fr) * 2016-11-17 2018-05-24 Exxonmobil Research And Engineering Company Procédé de conversion de gaz naturel en éther de diméthyle
CN107673309A (zh) * 2017-09-19 2018-02-09 北京林业大学 一种天然气与生物质炭联产制备合成气的方法
DE102018110293A1 (de) * 2018-04-27 2019-10-31 Linde Aktiengesellschaft Verfahren und Vorrichtung zur Behandlung einer Ablauge
US11932536B2 (en) * 2019-06-13 2024-03-19 Robert John Sanger Hydrogen autothermal reforming process

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CA2737742C (fr) 2018-02-13
CN102165047A (zh) 2011-08-24
CN102165047B (zh) 2015-04-22
ES2637015T3 (es) 2017-10-10
CA2737742A1 (fr) 2010-04-01
RU2011117290A (ru) 2012-11-10
AU2009296206A1 (en) 2010-04-01
AU2009296206B2 (en) 2015-08-20
US20140170029A1 (en) 2014-06-19
WO2010037093A2 (fr) 2010-04-01
US20100086451A1 (en) 2010-04-08
WO2010037093A3 (fr) 2010-07-22
RU2505585C2 (ru) 2014-01-27
EP2342308A2 (fr) 2011-07-13
EP2342308A4 (fr) 2013-04-10
US8652223B2 (en) 2014-02-18

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